Molybdate activity

In a closed circulation system the decomposition of N2O on the divalent metal molybdates (activated in vacuum at 700 K) was measurable above 600 K. The initial... 

Self-activated molybdate phosphorus are described in [5.406]. The energy transfer that occurs in molybdates activated with Eu3+ is described in [5.388], [5.407],... 

When fine powders of vitreous silica, quartz, tridymite, cristobalite, coesite, and stishovite of known particle-size distribution and specific surface area are investigated for their solubility in aqueous suspensions, final concentrations at and below the level of the saturated concentration of molybdate-active silicic acid are established. Experimental evidence indicates that all final concentrations are influenced by surface adsorption of silicic acid. Thus, the true solubility, in the sense of a saturated concentration of silicic acid in dynamic equilibrium with the suspended silica modification, is obscured. Regarding this solubility, the experimental final concentration represents a more or less supersaturated state. Through adsorption, the normally slow dissolution rates of silica decrease further with increasing silicic acid concentrations. Great differences exist between the dissolution rates of the individual samples. 

Tn 1950 Weitz et al. (23) developed a sensitive colorimetric method to measure small amounts of oligomeric silicic acid in the presence of polymeric forms. Oligomeric acid in this sense comprises molecules up to hexameric chains of hydrated SiC>4 tetrahedrons, which react readily with ammonium molybdate. Hence, this fraction of a sol is frequently referred to as molybdate-active silicic acid. 

Hydrogen peroxide and organic hydroperoxides can be reduced by molybdate-activated iodide [Allen et al. 1952 reactions (13) and (14)]. The iodine atoms formed in these reactions combine to iodine which complexes with iodide [reactions (15) and (16)], and it is this I3- complex which is measured (s(3540 nm) = 25,000 dm3 mol-1 cm-1)... 

In other cases, thermal decomposition is used to prepare the active layer which is then activated either by a high temperature treatment in H2 atmosphere, or by in situ reduction under cathodic load. It has been reported that for molybdate-activated cathodes the latter procedure is less satisfactory than the former [153]. Thus, temperature, procedure of preparation and activation are all crucial parameters which can dramatically influence the final activity. 

The effect of basicity on the following catalysts for Claus reaction was investigated Chromosorb-A cobalt-molybdate activated alumina bauxite and Porasil. The base loadings were 1-6 wt %. 

Monosilicic acid is termed molybdate-active it reacts rapidly according to ... 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

The mechanism and rate of hydrogen peroxide decomposition depend on many factors, including temperature, pH, presence or absence of a catalyst (7—10), such as metal ions, oxides, and hydroxides etc. Some common metal ions that actively support homogeneous catalysis of the decomposition include ferrous, ferric, cuprous, cupric, chromate, dichromate, molybdate, tungstate, and vanadate. For combinations, such as iron and... 

Molybdate is also known as an inhibitor of the important enzyme ATP sulfurylase where ATP is adenosine triphosphate, which activates sulfate for participation in biosynthetic pathways (56). The tetrahedral molybdate dianion, MoO , substitutes for the tetrahedral sulfate dianion, SO , and leads to futile cycling of the enzyme and total inhibition of sulfate activation. Molybdate is also a co-effector in the receptor for steroids (qv) in mammalian systems, a biochemical finding that may also have physiological implications (57). 

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. 

Biomedical Uses. The molybdate ion is added to total parenteral nutrition protocols and appears to alleviate toxicity of some of the amino acid components in these preparations (see Mineral NUTRIENTS) (97). Molybdenum supplements have been shown to reduce iiitrosarnine-induced mammary carcinomas in rats (50). A number of studies have shown that certain heteropolymolybdates (98) and organometaUic molybdenum compounds (99) have antiviral, including anti-AIDS, and antitumor activity (see Antiviral agents Chemotherapeutics, anticancer). 

Both molybdate and orthophosphate are excellent passivators in the presence of oxygen. Molybdate can be an effective inhibitor, especially when combined with other chemicals. Orthophosphate is not really an oxidizer per se but becomes one ia the presence of oxygen. If iron is put iato a phosphate solution without oxygen present, the corrosion potential remains active and the corrosion rate is not reduced. However, if oxygen is present, the corrosion potential iacreases ia the noble direction and the corrosion rate decreases significantly. 

The catalysts are prepared by impregnating the support with aqueous salts of molybdenum and the promoter. In acidic solutions, molybdate ions are present largely in the form of heptamers, [Mo2024] , and the resulting surface species are beHeved to be present in islands, perhaps containing only seven Mo ions (100). Before use, the catalyst is treated with H2 and some sulfur-containing compounds, and the surface oxides are converted into the sulfides that are the catalyticaHy active species. 

Dehydrogenation, Ammoxidation, and Other Heterogeneous Catalysts. Cerium has minor uses in other commercial catalysts (41) where the element s role is probably related to Ce(III)/Ce(IV) chemistry. Styrene is made from ethylbenzene by an alkah-promoted iron oxide-based catalyst. The addition of a few percent of cerium oxide improves this catalyst s activity for styrene formation presumably because of a beneficial interaction between the Fe(II)/Fe(III) and Ce(III)/Ce(IV) redox couples. The ammoxidation of propjiene to produce acrylonitrile is carried out over catalyticaHy active complex molybdates. Cerium, a component of several patented compositions (42), functions as an oxygen and electron transfer through its redox couple. 

Carbon monoxide has been found to poison cobalt molybdate catalysts. It causes not only instantaneous deactivation but a cumulative deactivation as well. It should be removed from treat gas entirely or at least reduced to a very low value. Carbon dioxide also must be removed since it is converted to CO in the reducing atmosphere employed in Hydrofining. Liquid water can damage the structural integrity of the catalyst. Water, in the form of steam does not necessarily hurt the catalyst. In fact 30 psig steam/air mixtures are used to regenerate the catalyst. Also, steam appears to enhance the catalyst activity in... 

In treating cracked stocks such as steam cracked naphtha or visbreaker naphtha, which are highly olefinic in nature, nickel molybdate or nickel tungstate catalysts are generally employed. These catalysts have much higher activity for olefin samration reactions than does cobalt molybdate. 

There has been much activity in this field of corrosion inhibition in recent years which appears to have been prompted by health and safety requirements. As with engine coolants, the use of nitrites, particularly where amines may also be present, needs to be considered carefully. Nitrites have been widely used in cutting, grinding, penetrating, drawing and hydraulic oils. Suggested replacements for nitrites and/or amines make use, inter alia, of various borate compounds, e.g. monoalkanolamide borates. Molybdates have also been proposed in conjunction with other inhibitors, e.g. carbox-ylates, phosphates, etc . Water-based metalworking fluids usually contain other additives in addition to corrosion inhibitors, e.g. for hard-water stability, anti-foam, bactericidal proderties and so on. Thus, claims are made for oil-in-water emulsions with bactericidal and anti-corrosion properties. 

The use of molybdenum catalysts in combination with hydrogen peroxide is not so common. Nevertheless, there are a number of systems in which molybdates have been employed for the activation of hydrogen peroxide. A catalytic amount of sodium molybdate in combination with monodentate ligands (e.g., hexaalkyl phosphorus triamides or pyridine-N-oxides), and sulfuric acid allowed the epoxidation of simple linear or cyclic olefins [46]. The selectivity obtained by this method was quite low, and significant amounts of diol were formed, even though highly concentrated hydrogen peroxide (>70%) was employed. 

The structure of the single phase bismuth-iron molybdate compound of composition Bl3FeMo20.2 related to the scheellte structure of Bi2Mo30-2( ). It is reported(, ) that the catalytic activity and selectivity of bismuth-iron molybdate for propylene oxidation and ammoxidatlon is not greater than that of bismuth molybdate. 

Table II. Catalytic Activity for Propylene Ammoxidation Over Bismuth-Iron Molybdate...

Analytical electron microscopy permits structural and chemical analyses of catalyst areas nearly 1000 times smaller than those studied by conventional bulk analysis techniques. Quantitative x-ray analyses of bismuth molybdates are shown from lOnm diameter regions to better than 5% relative accuracy for the elements 61 and Mo. Digital x-ray images show qualitative 2-dimensional distributions of elements with a lateral spatial resolution of lOnm in supported Pd catalysts and ZSM-5 zeolites. Fine structure in CuLj 2 edges from electron energy loss spectroscopy indicate d>ether the copper is in the form of Cu metal or Cu oxide. These techniques should prove to be of great utility for the analysis of active phases, promoters, and poisons. 

Several previous studies have demonstrated the power of AEH in various catalyst systems (1-11). Often AEM can provide reasons for variations in activity and selectivity during catalyst aging by providing information about the location of the elements involved in the active catalyst, promoter, or poison. In some cases, direct quantitative correlations of AEM analysis and catalyst performance can be made. This paper first reviews some of the techniques for AEM analysis of catalysts and then provides some descriptions of applications to bismuth molybdates, Pd on carbon, zeolites, and Cu/ZnO catalysts. 

The activity shown by unsupported Mo sulfide or Co molybdate catalysts W Is not Inconsistent with the nature of the active sites postulated. The essential pair members and Interactions could all exist on unsupported catalysts. Either Co or Mo alone can cause desulfurization. The support serves mainly to Increase the amount of exposed Co and Mo In some desirable configuration. 

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